CN101250313A - Nano-particle compound and preparation method thereof - Google Patents
Nano-particle compound and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nano particle compound and a preparation process thereof. The nano particle compound which is provided by the invention is formed by aquogel microsphere and inorganic nano particles, wherein the inorganic nano particles are jogged in the aquogel microsphere, the aquogel microsphere is isopropyl acrylamide and acroleic acid copolymer aquogel microsphere. The preparation process of nano particle compound comprises following steps that firstly preparing isopropyl acrylamide and acroleic acid copolymer aquogel microsphere, and dispersing aquogel microsphere into water, and dispersing inorganic nano particles into water, secondly mixing two kinds water solution which are obtained in first step, wherein the mass ratio of isopropyl acrylamide and acroleic acid copolymer aquogel microsphere and inorganic nano particle in mixing solution is 1:10-1:20, stirring mixing solution for 5-10 minutes under the conditions of temperature is 25-35 DEG C, and pH is 5-7, thereby obtaining nano particle compound.
Description
Technical field
The present invention relates to a kind of nano-particle compound and preparation method thereof.
Background technology
Metal nanoparticle has quantum size effect, surface interface effect, volume effect and macro quanta tunnel effect, make it have unique heat, electricity, magnetic and optical property etc., use thereby all have extremely widely such as aspects such as bio-sensing, catalysis, opto-electronic device and magnetic storages in a lot of fields.These performances that metal nanoparticle had all are based on its little yardstick, yet the metal nanoparticle system has very high specific surface energy usually, and change along with the residing environment of metal nanoparticle such as factors such as temperature, pH, ionic strength, shelf-time, nanoparticle is very easy to assemble, take place in case assemble, the metal nanoparticle system has just lost the special performance that many nanoparticle systems had, thereby has limited the application of metal nanoparticle.Therefore, how to prevent that its reunion from being a focus of metal nanoparticle architectural study.
Present a kind of effective means is to add stablizer in preparation process, makes between the metal nanoparticle to produce the effect that electrostatic repulsion forces or sterically hindered repulsive force reach the stable metal nanoparticle.Stablizer can be mineral ion, organic ion, organic solvent, tensio-active agent and polymkeric substance etc.From bibliographical information, the method that extensively adopts is to utilize silicon-dioxide or water-soluble polymers that metal nanoparticle is coated at present, thereby makes these nanoparticles possess good water dispersible and stability.The research synthetic and stable mechanism of the polymkeric substance of novel stabilization becomes the research focus in this field.
Summary of the invention
The purpose of this invention is to provide a kind of nano-particle compound and preparation method thereof.
Nano-particle compound provided by the present invention is made up of hydrogel microsphere and inorganic nano-particle, and described inorganic nano-particle is embedded in the described hydrogel microsphere;
Described hydrogel microsphere is N-isopropylacrylamide and acrylic copolymer hydrogel microsphere.
Wherein, the cross-linking density of described N-isopropylacrylamide and acrylic copolymer hydrogel microsphere (linking agent and monomeric mass ratio, monomer is a N-isopropylacrylamide herein) is 4.5wt.%～15wt.%; Linking agent in described N-isopropylacrylamide and the acrylic copolymer hydrogel microsphere is the methylene-bis N-isopropylacrylamide.
The median size of described inorganic nano-particle is below the 20nm; Described inorganic nano-particle is water miscible metal oxide nanoparticles, metal telluride nanoparticle or metal nanoparticle; Concrete metal oxide nanoparticles can be ferriferrous oxide nano-particle, and the metal telluride nanoparticle can be cadmium telluride quantum dot, and metal nanoparticle specifically can be golden nanometer particle.
The median size of described ferriferrous oxide nano-particle is 8～12nm, and the median size of described cadmium telluride quantum dot is 3～6nm, and the median size of described golden nanometer particle is 16～20nm.
The method for preparing nano-particle compound provided by the present invention may further comprise the steps:
1) preparation N-isopropylacrylamide and acrylic copolymer hydrogel microsphere and the hydrogel microsphere that obtains is scattered in the water; Inorganic nano-particle is scattered in the water;
2) two kinds of aqueous solution that step 1) obtained make that the mass ratio of N-isopropylacrylamide and acrylic copolymer hydrogel microsphere and inorganic nano-particle is 1: 10～1: 20 in the described mixing solutions; Is 25～35 ℃ with described mixing solutions in temperature, stirs under the condition of pH 5～7 5～10 minutes, obtains nano-particle compound.
Described method also can comprise the step of the nano-particle compound that obtains being carried out centrifugation and washing.Wherein, centrifugal speed is 6000 rev/mins, and centrifugation time is 10～30 minutes, and the nano-particle compound that obtains can be scattered in the water to be preserved.
Described N-isopropylacrylamide and acrylic copolymer hydrogel microsphere adopt the preparation of emulsifier-free emulsion polymerization method, and cross-linking density is 4.5wt.%～15wt.%; Linking agent in described N-isopropylacrylamide and the acrylic copolymer hydrogel microsphere can be the methylene-bis N-isopropylacrylamide.In the preparation process, can control the cross-linking density of N-isopropylacrylamide and acrylic copolymer hydrogel microsphere by the amount that adds linking agent.
The median size of described inorganic nano-particle is below the 20nm; Described inorganic nano-particle is water miscible metal oxide nanoparticles, metal telluride nanoparticle or metal nanoparticle; Concrete metal oxide nanoparticles can be ferriferrous oxide nano-particle, and the metal telluride nanoparticle can be cadmium telluride quantum dot, and metal nanoparticle specifically can be golden nanometer particle.
The median size of described ferriferrous oxide nano-particle is 8～12nm, and the median size of described cadmium telluride quantum dot is 3～6nm, and the median size of described golden nanometer particle is 16～20nm.
In the method for preparing nano-particle compound provided by the invention, the N-isopropylacrylamide of employing and acrylic copolymer hydrogel microsphere and inorganic nano-particle all are scattered in the water, have avoided the use of organic solvent.Because hydrogel microsphere contains N-isopropylacrylamide unit and acrylic acid units, so this hydrogel microsphere has the advantages that temperature and pH double-bang firecracker are answered.The size in hydrogel microsphere cross-linked network hole can be regulated and control by the add-on of linking agent.Research different from the past, inorganic nano-particle is present in the middle of the network of macromolecule hydrogel among the present invention, thereby makes inorganic nano-particle have good weather, resistance to acids and bases, and storage that can the long period.Preparation method provided by the invention is reliable, and operation steps is simple, and institute responds and all carries out in aqueous phase.This method has broad application prospects in the preparation field of polymer/inorganic nanometer hybrid material.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) image of embodiment 1 ferriferrous oxide nano-particle mixture
Fig. 2 is transmission electron microscope (TEM) image of embodiment 2 ferriferrous oxide nano-particle mixtures
Fig. 3 is transmission electron microscope (TEM) image of embodiment 3 ferriferrous oxide nano-particle mixtures
Fig. 4 is the fluorescence microscope images of embodiment 4 cadmium telluride quantum dot mixtures
Fig. 5 is transmission electron microscope (TEM) image of embodiment 5 golden nanometer particle mixtures
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Embodiment 1
1) the preparation cross-linking density is N-isopropylacrylamide and the acrylic copolymer hydrogel microsphere of 4.5wt.-%:
Adding 20 ml waters, 0.176 gram N-isopropylacrylamide, quality are the methylene-bis N-isopropylacrylamide of the 4.5wt.-% of N-isopropylacrylamide quality in 100 milliliters of three-necked bottles of agitator, thermometer are housed; 10 μ L (0.01g) vinylformic acid; stirring also charged into the nitrogen deoxygenation 30 minutes; be warming up to 70 ℃; 0.004 gram ammonium persulphate is dissolved in and joins then in 5 ml waters in the above-mentioned solution, in nitrogen protection reaction 4 hours down.Gained solution was dialysed for two weeks in deionized water, supernatant liquid is poured out in centrifugation then (10000 rev/mins), and centrifugation is dissolved in water, repeat aforesaid operations three times, promptly get N-isopropylacrylamide and acrylic copolymer hydrogel microsphere that cross-linking density is 4.5wt.-%.
2) preparation ferriferrous oxide nano-particle:
Get 24 gram FeCl
36H
2O and 9.82 gram FeCl
24H
2O is dissolved in 100 ml waters, is warming up to 80 ℃ and 50 milliliters of ammoniacal liquor of rapid adding under nitrogen protection, and solution becomes black at once.React after 30 minutes to add 3.76 gram oleic acid in above-mentioned solution, keep solution temperature to continue reaction 1.5 hours at 80 ℃, final product is washed till neutrality with deionized water and is scattered in the water.The median size of prepared ferriferrous oxide nano-particle is 10 ± 2 nanometers.
3) preparation ferriferrous oxide nano-particle mixture
N-isopropylacrylamide and the acrylic copolymer hydrogel microsphere (cross-linking density is 4.5wt.-%) of step 1) preparation of getting 1mL concentration and be 0.1wt% is in 10mL single port bottle, and adding 3mL concentration is 0.006gmL under the stirring condition
-1Step 2) aqueous solution of Zhi Bei ferriferrous oxide nano-particle, make that the mass ratio of N-isopropylacrylamide and acrylic copolymer hydrogel microsphere and nanoparticle is 1: 18 in the mixing solutions, above-mentioned mixed solution under being 25 ℃, the condition of pH 7, temperature is continued to stir 5～10 minutes, centrifugation then, 6000 rev/mins of rotating speeds, the product deionized water wash, repeated washing three times gets the ferriferrous oxide nano-particle mixture.The ferriferrous oxide nano-particle mixture that obtains is scattered in the water, and gets an amount of sample drop and be added on the copper mesh that is covered with the carbon supporting film, dry back is analyzed with transmission electron microscope.The result as shown in Figure 1.As seen from the figure, charge capacity height, dispersiveness and the good stability of ferriferrous oxide nano-particle on hydrogel microsphere in the ferriferrous oxide nano-particle mixture of embodiment 1 preparation.
Embodiment 2
1) the preparation cross-linking density is N-isopropylacrylamide and the acrylic copolymer hydrogel microsphere of 10wt.-%:
Adding 20 ml waters, 0.176 gram N-isopropylacrylamide, quality are the methylene-bis N-isopropylacrylamide of the 10wt.-% of N-isopropylacrylamide quality in 100 milliliters of three-necked bottles of agitator, thermometer are housed; 10 μ L (0.01g) vinylformic acid; stirring also charged into the nitrogen deoxygenation 30 minutes; be warming up to 70 ℃; 0.004 gram ammonium persulphate is dissolved in and joins then in 5 ml waters in the above-mentioned solution, in nitrogen protection reaction 4 hours down.Gained solution was dialysed for two weeks in deionized water, supernatant liquid is poured out in centrifugation then (10000 rev/mins), and centrifugation is dissolved in water, repeat aforesaid operations three times, promptly get N-isopropylacrylamide and acrylic copolymer hydrogel microsphere that cross-linking density is 10wt.-%.
2) preparation ferriferrous oxide nano-particle:
With embodiment 1 step 2).
3) preparation ferriferrous oxide nano-particle mixture:
N-isopropylacrylamide and the acrylic acid copolymer hydrogel microballoon (cross-linking density is 10wt.-%) of step 1) preparation of getting 1mL concentration and be 0.1wt% is in 10mL single port bottle, and adding 3mL concentration is 0.006gmL under the stirring condition
-1Step 2) aqueous solution of Zhi Bei ferriferrous oxide nano-particle, make that the mass ratio of N-isopropylacrylamide and acrylic copolymer hydrogel microsphere and nanoparticle is 1: 18 in the mixing solutions, above-mentioned mixed solution under being 25 ℃, the condition of pH 7, temperature is continued to stir 5～10 minutes, centrifugation then, 6000 rev/mins of rotating speeds, the product deionized water wash, repeated washing three times gets the ferriferrous oxide nano-particle mixture.The ferriferrous oxide nano-particle mixture that obtains is scattered in the water, and gets an amount of sample drop and be added on the copper mesh that is covered with the carbon supporting film, dry back is analyzed with transmission electron microscope.The result as shown in Figure 2.As seen from the figure, the charge capacity of ferriferrous oxide nano-particle on hydrogel microsphere is higher in the ferriferrous oxide nano-particle mixture of embodiment 2 preparations, dispersiveness and good stability.
Embodiment 3
1) the preparation cross-linking density is N-isopropylacrylamide and the acrylic copolymer hydrogel microsphere of 15wt.-%:
Adding 20 ml waters, 0.176 gram N-isopropylacrylamide, quality are the methylene-bis N-isopropylacrylamide of the 15wt.-% of N-isopropylacrylamide quality in 100 milliliters of three-necked bottles of agitator, thermometer are housed; 10 μ L (0.01g) vinylformic acid; stirring also charged into the nitrogen deoxygenation 30 minutes; be warming up to 70 ℃; 0.004 gram ammonium persulphate is dissolved in and joins then in 5 ml waters in the above-mentioned solution, in nitrogen protection reaction 4 hours down.Gained solution was dialysed for two weeks in deionized water, supernatant liquid is poured out in centrifugation then (10000 rev/mins), and centrifugation is dissolved in water, repeat aforesaid operations three times, promptly get N-isopropylacrylamide and acrylic copolymer hydrogel microsphere that cross-linking density is 15wt.-%.
2) preparation ferriferrous oxide nano-particle:
With embodiment 1 step 2).
3) preparation ferriferrous oxide nano-particle mixture:
N-isopropylacrylamide and the acrylic acid copolymer hydrogel microballoon (cross-linking density is 15wt.-%) of step 1 preparation of getting 1mL concentration and be 0.1wt% is in 10mL single port bottle, and adding 3mL concentration is about 0.006gmL under the stirring condition
-1Step 2) aqueous solution of Zhi Bei ferriferrous oxide nano-particle, make that the mass ratio of N-isopropylacrylamide and acrylic copolymer hydrogel microsphere and nanoparticle is 1: 18 in the mixing solutions, above-mentioned mixed solution under being 25 ℃, the condition of pH 7, temperature is continued to stir 5～10 minutes, centrifugation then, 6000 rev/mins of rotating speeds, the product deionized water wash, repeated washing three times gets the ferriferrous oxide nano-particle mixture.The ferriferrous oxide nano-particle mixture that obtains is scattered in the water, and gets an amount of sample drop and be added on the copper mesh that is covered with the carbon supporting film, dry back is analyzed with transmission electron microscope.The result as shown in Figure 3.As seen from the figure, the charge capacity of ferriferrous oxide nano-particle on hydrogel microsphere is that the hydrogel microsphere of 4.5wt% and 10wt% decreases than cross-linking density in the ferriferrous oxide nano-particle mixture of embodiment 3 preparation, but dispersiveness and good stability.
Embodiment 4
1) the preparation degree of crosslinking is N-isopropylacrylamide and the acrylic copolymer hydrogel microsphere of 4.5wt.-%:
With embodiment 1 step 1).
2) preparation cadmium telluride quantum dot:
Keep CdCl in the reaction process
2, TGA (Thiovanic acid) and NaHTe mol ratio be 1: 1.5: 0.5.Specific as follows: as in 25 milliliters there-necked flask, to add 0.1 gram NaBH
4With 5 gram water, add 0.158 gram Te powder then, react on 0 ℃, nitrogen protection was reacted 48 hours down, thereby obtained the aqueous solution of NaHTe.Get TGA (Thiovanic acid) and join CdCl
2The aqueous solution in and to regulate pH with 0.1MNaOH be 10, the concentration that makes final Cd presoma is 10mM.The aqueous solution with NaHTe joins in the above-mentioned solution then, gets 50 milliliters of mixing solutionss and reacts 1～2 hour under 180 ℃ of conditions in stainless steel cauldron, promptly gets cadmium telluride quantum dot.The median size of prepared cadmium telluride quantum dot is 3～6 nanometers.
3) preparation cadmium telluride quantum dot mixture:
Get 1mL concentration and be the N-isopropylacrylamide of step 1) of 0.1wt% and acrylic acid copolymer hydrogel microballoon (cross-linking density is 4.5wt.-%) in 10mL single port bottle, add 3mL concentration under the stirring condition and be about 0.004gmL
-1Cadmium telluride quantum dot, make that the mass ratio of N-isopropylacrylamide and acrylic copolymer hydrogel microsphere and nanoparticle is 1: 12 in the mixing solutions, above-mentioned mixed solution under being 25 ℃, the condition of pH 7, temperature is continued to stir 5～10 minutes, centrifugation then, 6000 rev/mins of rotating speeds, the product deionized water wash, repeated washing three times gets the cadmium telluride quantum dot mixture.The cadmium telluride quantum dot mixture that obtains is scattered in the water, and gets an amount of sample drop and be added on the slide glass, carry out fluorescence microscope after the drying.
Analyze the cadmium telluride quantum dot mixture with fluorescent microscope.Fluorescence micrograph as shown in Figure 4.As seen from the figure, the charge capacity of cadmium telluride quantum dot on hydrogel microsphere is higher in the cadmium telluride quantum dot mixture of embodiment 4 preparations, and stability and dispersion effect are good.
Embodiment 5
1) the preparation cross-linking density is N-isopropylacrylamide and the acrylic copolymer hydrogel microsphere of 4.5wt.-%:
With embodiment 1 step 1)
2) preparation golden nanometer particle:
With the 100mL mass percent concentration is the HAuCl of 0.01wt%
4Solution is heated to boiling, adds the trisodium citrate aqueous solution that the 4mL mass percent concentration is 1wt% rapidly, begins some blueness, and is light blue then, blue, and reheat occurs red, boils 7～10min and occur transparent orange red.Stopped reaction obtains water miscible golden nanometer particle.The median size of prepared golden nanometer particle is 18 ± 2 nanometers.
3) preparation golden nanometer particle mixture:
Adding 1mL concentration in 10mL single port bottle is the N-isopropylacrylamide and the acrylic copolymer hydrogel microsphere (cross-linking density is 4.5wt.-%) of the step 1) of 0.1wt%, adds 3mL concentration under the stirring condition and is about 0.005gmL
-1Golden nanometer particle continues above-mentioned mixed solution to stir 5～10 minutes under temperature is 25 ℃, the condition of pH 7, centrifugation then, and 6000 rev/mins of rotating speeds, the product deionized water wash, repeated washing three times must the golden nanometer particle mixture.The golden nanometer particle mixture that obtains is scattered in the water, and gets an amount of sample drop and be added on the copper mesh that is covered with the carbon supporting film, carry out transmission electron microscope observation after the drying.
With tem study golden nanometer particle mixture.The result as shown in Figure 5.As seen from the figure, the charge capacity height of golden nanometer particle on hydrogel microsphere in the golden nanometer particle mixture of embodiment 5 preparations, dispersion effect is good.
Claims (10)
1, a kind of nano-particle compound is made up of hydrogel microsphere and inorganic nano-particle, and described inorganic nano-particle is embedded in the described hydrogel microsphere;
Described hydrogel microsphere is N-isopropylacrylamide and acrylic copolymer hydrogel microsphere.
2, nano-particle compound according to claim 1 is characterized in that: the cross-linking density of described N-isopropylacrylamide and acrylic copolymer hydrogel microsphere is 4.5wt.%～15wt.%; The linking agent of described N-isopropylacrylamide and acrylic copolymer hydrogel microsphere is the methylene-bis N-isopropylacrylamide.
3, nano-particle compound according to claim 1 and 2 is characterized in that: the median size of described inorganic nano-particle is below the 20nm; Described inorganic nano-particle is water miscible metal oxide nanoparticles, metal telluride nanoparticle or metal nanoparticle; Wherein, metal oxide nanoparticles is preferably ferriferrous oxide nano-particle; The metal telluride nanoparticle is preferably cadmium telluride quantum dot; Metal nanoparticle is preferably golden nanometer particle.
4, nano-particle compound according to claim 3, it is characterized in that: the median size of described ferriferrous oxide nano-particle is 8～12nm, the median size of described cadmium telluride quantum dot is 3～6nm, and the median size of described golden nanometer particle is 16～20nm.
5, a kind of method for preparing arbitrary described nano-particle compound among the claim 1-4 may further comprise the steps:
1) preparation N-isopropylacrylamide and acrylic copolymer hydrogel microsphere and the hydrogel microsphere that obtains is scattered in the water; Inorganic nano-particle is scattered in the water;
2) two kinds of aqueous solution that step 1) obtained make that the mass ratio of N-isopropylacrylamide and acrylic copolymer hydrogel microsphere and inorganic nano-particle is 1: 10～1: 20 in the described mixing solutions; Is 25～35 ℃ with described mixing solutions in temperature, stirs under the condition of pH 5～7 5～10 minutes, obtains nano-particle compound.
6, method according to claim 5 is characterized in that: described method also comprises the step of the nano-particle compound that obtains being carried out centrifugation and washing.
7, according to claim 5 or 6 described methods, it is characterized in that: the cross-linking density of described N-isopropylacrylamide and acrylic copolymer hydrogel microsphere is 4.5wt.%～15wt.%; The linking agent of described N-isopropylacrylamide and acrylic copolymer hydrogel microsphere is the methylene-bis N-isopropylacrylamide.
8, according to the arbitrary described method of claim 5～7, it is characterized in that: the median size of described inorganic nano-particle is below the 20nm; Described inorganic nano-particle is water miscible metal oxide nanoparticles, metal telluride nanoparticle or metal nanoparticle; Wherein, metal oxide nanoparticles is preferably ferriferrous oxide nano-particle; The metal telluride nanoparticle is preferably cadmium telluride quantum dot; Metal nanoparticle is preferably golden nanometer particle.
9, nano-particle compound according to claim 8, it is characterized in that: the median size of described ferriferrous oxide nano-particle is 8～12nm, the median size of described cadmium telluride quantum dot is 3～6nm, and the median size of described golden nanometer particle is 16～20nm.
10, according to the arbitrary described nano-particle compound of claim 1～4, it is characterized in that: described nano-particle compound is according to the arbitrary described method preparation of claim 5～9.
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